Organosiloxanes



Patented Oct. 31, 1950 ORGANOSILOXANES John T. Go,odwin, .lr., Midland, Mich, assignor to Dow Corning Corporation, Midland, Mich, a

corporation of Michigan No Drawing. Application March 19,1949, I SerialNo. 82,476

. 9 Claims. 1 The present invention relates to the production of polymeric organosilicon compositions.

The present organosilicon industry is'based upon siloxanes which are materials inv which the silicon atoms are linked by oxygen atoms. In

another type of silicon compound the silicon atoms are linkeddirectly to .each'other. In a third type the silicon atoms are linked by organic radicals.

Objects of the present invention are to produce polymeric organosili-con compounds in which some pairs or silicon atoms are linked by methylene radicals and others by oxygen atoms. Other objects and. advantages of the present invention will be apparent from the following description and the subjoined claims.

In accordance with the process of the present invention, organosilicon compositions are produced by the hydrolysis and condensation of compounds of the type. R(R2SiCH2)nSiRY2, where each R is a hydrocarbon radical of the group consisting of alkyl radicals such as methyl to octadecyl and monocyclic aryl radicals, such as phenyl, tolyl and xylyl, and Y is a substituent of the group consisting of alkoxy radicals and halogen atoms. These compositions contain both methylene radicals and oxygen atoms linking the silicon atoms.

The products obtained by the hydrolysis and condensation in accord herewith are fluids. They are polymers, the polymeric units of which consist of units of the type in which each R is a radical of the group consisting of alkyl and monocyclicaryl radicals and m is an integer having a value of from 1 to 2 inclusive. Where the compounds contain 3 of these units both cis and trans isomers have been obtained. As is well known from the chemistry of the difunctional siloxanes, these materials hereof may :be cyclic or linear polymers;-

The intermediate in the case of (CH3) 3SiCH2SiCH3 (OC2H5) 2 pound (QHflsSiCI-IzSKCI-BMCI; by contacting the former with an alkali metal in the presence of the latter compound. j

The intermediates of the type RaSiCI-ISiRXz,

hydrolyzed and condensed in accord-herewith; may also be'preparedby reacting a'comp'ound'- of the type XzRSiCI-IzSiRX in liquid phase with a Grignard reagent of the type RMgX in which" each R represents a radical of the group consisting of alkyl and monocyclicaryl radicals and. each X represents a halogen atom.

The methods of preparing the intermediates are claimed in my copending application, Serial Number 82,480, now U. S. Patent 2,507,520, filed .used to prepare the polymers in accord herewith. If desired, an acid or alkaline catalyst may be 3 used. The direct product of the hydrolysisis the may be prepared by reacting the compound an alkali metal in the presence of the latter compound. If the intermediate CH3 (CH3) 2SiCH2 2SiCH3 (OCzHs) 2 is desired, it may be prepared by reacting the compound C1CH2SiCH3(OC2H5)2 and the com- 'filtered, and distilled. Upon distillation,

silanol, but this condenses readily upon standing to produce the polymers in accord herewith.

The polymers produced by the hydrolysis and condensation hereof are of a wide range of utility. They are of utility for such purposes as hydrophobing agents, lubricants, hydraulic fluids, heat transfer media, and thermal expansion regulator fluids, and are of greater stability than siloxanes free of methylene linkages.

The following examples illustrate the method of the present invention.

Example 1 A mixture of parts by Weight of (CI-I3) BSiCHzSiCI-Is (0021 15) i 63.9 parts of percent ethyl alcohol, and 100.79 parts of 35% HCl was refluxed for 20 hours. The acid-aqueous alcohol layer was drawn off, and the hydrolyzate washed with water, dried, 21.05 parts of a fluid identified as was obtained. This compound has a boiling point of 181 at 24 mm., a refractive index of 1.4391 at 25 C., a density of 0.9151 at 25 C. and a specific refraction of 0.2870. Distillation also yielded 23.48 parts of a fluid which was identified as cnpzsicms ionzo-qi This compound has a boiling point of 223 C. at

24 mm., a refractive index of 1.4452 at 25 C., a"

density of 0.9390 at 25 C., and a specific retrac tion of 0.2870.

3 Example 2 A mixture of 57 parts by weight of CH3 (CH3) 2SiCH2] 2 SiCH3 (OCzI-Is) 2 and 72.5 parts of 10% (vol.) H2804 was refluxed for 6 hours. The acid-water layer was drawn ofi and the hydrolyzate washed with water, dried over NazCOa, and filtered. Distillation yieldc 23.02 parts of a fluid identified as This compound has a boiling point of 252 C. at 25 mm., a refractive index of 1.4598 at 25 C., a

density of 0.9208 at 25 C., and a specific refraction of 0.2972. 7

Example 3 A mixture of 80 parts by weight of (CH3)3SiCH2SiCH3(OC2H5)2 63.98 parts of 95% C2H5OH, and 100.79 parts of 35%, HCl was refluxed for 20 hours. The acidaqueous alcohol layer was drawn off and the hydrolyzate washed with H2O. The washings and the original water layer were extracted with ben- 'zene.. The benzene extract was then' filtered.

Distillation yielded 21.05 parts of [(CH3)3SiCH2 llCH30-]3 and 23.48 parts of a fluid mixture of omnsmmsrcmoq.

and"

C2H50[ (CI-I3) BSiCHzSiCHsOlsCzHs Both of these compounds have a boiling point of 223 C. at 24 mm.

Example 4 82 parts by weight of (CH3)3SiCH2SiCH3C12 and 100 partsof 10% H2804 were mixed and refluxed for 7 hours. The acid-water layer was drawn oil? and the hydrolyzate washed with H2O, dried over anhydrous Na2SO4, and filtered. The filtrate was then distilled. '15 parts of were obtained. This pentamer is a fluid having a boiling point of 270 C. at 25 mm., a refractive index of 1.4493 at 25 C., a density of 09303 at 25 (3., and a specific refraction of 0.2885. There remained 13 parts of a high molecular weight nonvolatile fluid polymer of the formula which contained cyclics of this formula in which 11. had values up to 10.

Example 145 parts by weight of (CI-I3) zCsHsSiCI-IzSiCI-Is (0021-15) 2 was shaken with water. The excess water was taken oil. The hydrolyzate was Washed several times with H2O, thinned with benzene, and dried over anhydrous NazCOs. The benzene was boiled off. The reaction mixture was refluxed for one hour. 70 parts of unreacted material was recoveredlby distillation, leaving 42 parts of product. This'product was a mixture of compounds of the type [(CH3)zCtHaSiCH2sli OH30-]n (1948) pages 30683071.

4 and had a refractive index of 1.3183 at 25 (3., and a density of 1.0356 at 25 0., and contained cyclic compounds in which n was equal to 3 and 4, as well as higher members.

Example 6 220 parts of (CH3)3SiCH2SiCH3(OC2H5)2 was hydrolyzed by adding 36 parts by weight of water. The hydrolyzate was dissolved in benzene. The hydrolyzate was washed with 100 parts of H20, dried over 02.003, filtered and distilled. Distillation yielded two compounds of the formula in which each R is a radical of the group consisting of alkyl and monocyclicaryl radicals and mis an integer having a value of from 1 to 2 inclusive.

2. Polymers in accordance with claim 1 in which R represents methyl.

3. Polymers in accordance with claim 1 in which all of the Rs are methyl and monocyclicaryl radicals and which polymers containflboth methyl and monocyclicaryl radicals.

4, '[oaHdoHmsioHisioHimin which n has a value from 3 to 4 inclusive.

5, cmhsioms icmo-t in which n has a value from 3 to 5 inclusive.

6 {CHs[(CHz)2SiCHzhfiiCHaO-la 7. The method which comprises hydrolyzing compounds of the type R(R2SiCH2) mSlRYZ in which each R is a radical of the group consisting of alkyl and monocyclicaryl radicals, m is an integer having a value of from 1 to 2 inclusive, and Y is a substituent of the group consisting of alkoxy radicals and halogen atoms, and condensing the hydrolysis product thereof, whereby to obtain organosilicon polymers, the polymeric units of which are of the type [R (RzSi 0H2) mSiiR o- 8. The method in accordance with claim'f in which only some of the Rs are methyl radicals and the remainder are monocyclicaryl radicals.

9. The method in accordance with claim 7 in which all of the Rs are methyl radicals.

' JOHN T. GOODWIN, Jr.

REFERENCE S CITED The following references are of record in the file of this patent: 7 2;.

Sommer: Jour. Am. Chem. Soc, vol. 69 (1947) page 980. r f

Goodwin: Jour. Am. Chem. Soc, vol. 69 (1947 page 2247. Bluestein: Jour. Am. Chem. 'Soc.,

vol. 70

Certificate of Correction Patent N 0. 2,527,808 October 31, 1950 JOHN T. GOODWIN, JR.

Column 2, line 38, for 63.9 parts read 163.98 parts; line 15, for that portion of the compound reading same may conform to the record of the case in the Patent Oflice Signed and sealed this 23rd day of January, A. D. 1951.

THOMAS F. MURPHY,

Assistqnt Gammz'ssz'oner of Patents. 

1. ORGANOSILICON POLYMERS, THE POLYMERIC UNITS OF WHICH CONSIST OF UNITS OF THE TYPE 